Ureas are widely used in drugs,materials and catalysts because of their diamide structure,which can form strong hydrogen bonds.Therefore,it is of great scientific significance to develop efficient and green methods fo...Ureas are widely used in drugs,materials and catalysts because of their diamide structure,which can form strong hydrogen bonds.Therefore,it is of great scientific significance to develop efficient and green methods for the synthesis of urea compounds,especially unsymmetrical ureas.Here,we have disclosed novel and highly efficient three-component coupling reactions of organic halides,sodium cyanate and amines enabled by nickel/photoredox dual catalysis for the preparation of unsymmetrical ureas.The reaction features simple and safe operations,broad substrate scopes,and product diversities.It allows the facile synthesis of N-aryl/vinyl ureas from readily available,user-friendly feedstocks under mild conditions(27 examples,36%—98%yields).In addition,this method is further derived to alcohols as nucleophiles to synthesize a series of carbamates(15 examples,40%—95%yields).The mechanism experiment shows that the isocyanate produced by the coupling of halide and sodium cyanate may be the key intermediate in this reaction.展开更多
Carbon dioxide is a ubiquitous and inexpensive one-carbon source for chemical synthesis, and the efficient incorporation of CO2 into organic molecules is of widespread research interest both for economic and ecologica...Carbon dioxide is a ubiquitous and inexpensive one-carbon source for chemical synthesis, and the efficient incorporation of CO2 into organic molecules is of widespread research interest both for economic and ecological reasons. The methodologies to employ carbon dioxide as a single-carbon unit to construct molecules relevant for agrochemical and pharmaceutical research include many elegant approaches, including asymmetric transformations. Even though remarkable achievements have been made in the field of light-driven catalysis, especially photoredox catalysis, homogeneous light-driven catalytic carboxylation by employing CO2 as the key reagent has only become a subject of increasing attention in recent years. Therefore, this concise review will discuss the latest advances in this research area.展开更多
A new efficient synthesis of 2,5,6-trisubstituted oxazolo（5,4-d]pyrimidi-7（6H）-ones by consecutive azaWittig reaction was developed.The sequential three-component reaction of oxazolyliminophosphorane4,isocyanates a...A new efficient synthesis of 2,5,6-trisubstituted oxazolo（5,4-d]pyrimidi-7（6H）-ones by consecutive azaWittig reaction was developed.The sequential three-component reaction of oxazolyliminophosphorane4,isocyanates and amines produced 2,5,6-trisubstituted oxazolo[5,4-d]pyrimidi-7（6H）-ones 7 in good overall yields in the presence of catalytic amount of EtONa.展开更多
The rapid collection of a library of biologically relevant molecules is essential in new drug discovery.Here we show a variety of bioactive 1,3-indanedione-based spirocyclic tetrahydroquinolines that have been concise...The rapid collection of a library of biologically relevant molecules is essential in new drug discovery.Here we show a variety of bioactive 1,3-indanedione-based spirocyclic tetrahydroquinolines that have been concisely and efficiently constructed under the guidance of biology-oriented synthesis(BIOS).Using Pd(PPh_(3))_(4) as a catalyst,various 2-arylidene-1,3-indanediones can react with vinyl benzoxazinanones under the mild condition to afford a new class of spirocyclic tetrahydroquinolines in moderate to excellent yields(45%-99%)with high stereocontrol(>95:5 diastereoselectivity).Their structures were unambiguously confirmed by X-ray single crystal analysis.The biological evaluation revealed that two of the 1,3-indanedione-based spirocyclic tetrahydroquinolines show remarkable apoptosis-inducing activities over A549 human lung cancer cells,exceeding that of cisplatin.The antitur activities were triggered by reactive oxygen species,commonly overproduced in cancer cells.The clinical demand for antitumor chemotherapy for lung cancer has encouraged an all-out search for analogues with lower toxcity,improved therapeutic index and increased activity.展开更多
Bicyclo[1.1.1]pentane (BCP) scaffolds can serve as bioisosteres of phenyl, tert-butyl and alkyne groups which are widely used in medicinal chemistry today [1]. Replacing para-phenyl rings in most of pharmaceutical can...Bicyclo[1.1.1]pentane (BCP) scaffolds can serve as bioisosteres of phenyl, tert-butyl and alkyne groups which are widely used in medicinal chemistry today [1]. Replacing para-phenyl rings in most of pharmaceutical candidates with 1,3-disubstituted BCP moieties will improve their biological activities and physico-chemical profiles[2].展开更多
基金the National Natural Science Foundation of Chinaa(Nos.22271113,92256301,21822103,91956201,21820102003 and 21602052)the Natural Science Foundation of Hubei Province(No.2022CFB413)the fund from Central China Normal University for support of this research.
文摘Ureas are widely used in drugs,materials and catalysts because of their diamide structure,which can form strong hydrogen bonds.Therefore,it is of great scientific significance to develop efficient and green methods for the synthesis of urea compounds,especially unsymmetrical ureas.Here,we have disclosed novel and highly efficient three-component coupling reactions of organic halides,sodium cyanate and amines enabled by nickel/photoredox dual catalysis for the preparation of unsymmetrical ureas.The reaction features simple and safe operations,broad substrate scopes,and product diversities.It allows the facile synthesis of N-aryl/vinyl ureas from readily available,user-friendly feedstocks under mild conditions(27 examples,36%—98%yields).In addition,this method is further derived to alcohols as nucleophiles to synthesize a series of carbamates(15 examples,40%—95%yields).The mechanism experiment shows that the isocyanate produced by the coupling of halide and sodium cyanate may be the key intermediate in this reaction.
基金We thank the National Natural Science Foundation of China （Nos. 21602052 and 21702151） for financial support.
文摘Carbon dioxide is a ubiquitous and inexpensive one-carbon source for chemical synthesis, and the efficient incorporation of CO2 into organic molecules is of widespread research interest both for economic and ecological reasons. The methodologies to employ carbon dioxide as a single-carbon unit to construct molecules relevant for agrochemical and pharmaceutical research include many elegant approaches, including asymmetric transformations. Even though remarkable achievements have been made in the field of light-driven catalysis, especially photoredox catalysis, homogeneous light-driven catalytic carboxylation by employing CO2 as the key reagent has only become a subject of increasing attention in recent years. Therefore, this concise review will discuss the latest advances in this research area.
基金financial support of this work by the National Natural Science Foundation of China(No.21172085)the Natural Science Foundation of Hubei Province(No. 2014CFB567)the Open Foundation of Hubei Province Key Laboratory of Purification and Application of Plant Anti-cancer Active Ingredients
文摘A new efficient synthesis of 2,5,6-trisubstituted oxazolo（5,4-d]pyrimidi-7（6H）-ones by consecutive azaWittig reaction was developed.The sequential three-component reaction of oxazolyliminophosphorane4,isocyanates and amines produced 2,5,6-trisubstituted oxazolo[5,4-d]pyrimidi-7（6H）-ones 7 in good overall yields in the presence of catalytic amount of EtONa.
基金Financial support from the National Natural Science Foundation of China(No.21602052)the start-up funding from Wuhan University(Nos.691000002 and 600460026)are gratefully acknowledged.The authors thank Prof.Dr.Xianggao Meng(Central China Normal University)for performing the X-ray crystal analysis.
文摘The rapid collection of a library of biologically relevant molecules is essential in new drug discovery.Here we show a variety of bioactive 1,3-indanedione-based spirocyclic tetrahydroquinolines that have been concisely and efficiently constructed under the guidance of biology-oriented synthesis(BIOS).Using Pd(PPh_(3))_(4) as a catalyst,various 2-arylidene-1,3-indanediones can react with vinyl benzoxazinanones under the mild condition to afford a new class of spirocyclic tetrahydroquinolines in moderate to excellent yields(45%-99%)with high stereocontrol(>95:5 diastereoselectivity).Their structures were unambiguously confirmed by X-ray single crystal analysis.The biological evaluation revealed that two of the 1,3-indanedione-based spirocyclic tetrahydroquinolines show remarkable apoptosis-inducing activities over A549 human lung cancer cells,exceeding that of cisplatin.The antitur activities were triggered by reactive oxygen species,commonly overproduced in cancer cells.The clinical demand for antitumor chemotherapy for lung cancer has encouraged an all-out search for analogues with lower toxcity,improved therapeutic index and increased activity.
基金the National Natural Science Foundation of China (21602052)。
文摘Bicyclo[1.1.1]pentane (BCP) scaffolds can serve as bioisosteres of phenyl, tert-butyl and alkyne groups which are widely used in medicinal chemistry today [1]. Replacing para-phenyl rings in most of pharmaceutical candidates with 1,3-disubstituted BCP moieties will improve their biological activities and physico-chemical profiles[2].
